CN105175599A - Preparing method for heat-resistant strong-base type anion exchange resin - Google Patents
Preparing method for heat-resistant strong-base type anion exchange resin Download PDFInfo
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- CN105175599A CN105175599A CN201510604651.6A CN201510604651A CN105175599A CN 105175599 A CN105175599 A CN 105175599A CN 201510604651 A CN201510604651 A CN 201510604651A CN 105175599 A CN105175599 A CN 105175599A
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Abstract
The invention discloses a preparing method for heat-resistant strong-base type anion exchange resin. The preparing method comprises the following steps that ceramic particles and a silane coupling agent are adopted for preparing a first precast material; a water phase and an oil phase are prepared, the oil phase is added into the water phase, and sulfur chloride is added continually to prepare a second precast material; the second precast material and bi-decyl alkyl tertiary amine are adopted to be mixed with 1,6-hexamethylenebis(dicyanamide) and sodium ethoxide to prepare a third precast material; the third precast material, nitrobenzene, anhydrous AlCl3, stearyl chloride, dodecyl chloride, aryl chloride and the first precast material are adopted for preparing the heat-resistant strong-base type anion exchange resin. The heat-resistant strong-base type anion exchange resin is extremely good in heat resisting performance.
Description
Technical field
The present invention relates to anionite-exchange resin technical field, particularly relate to a kind of preparation method of heat-resisting strong basic type anion-exchange resin.
Background technology
Strong anion-exchange resin is widely used for the fields such as water treatment, material purification, material decolouring, and the structure of strong alkali ion exchange resin, containing quaternary ammonium group, obtains with the chloromethyl that polystyrene phenyl ring connects and a part reactive tertiary amine; Due to the constructional feature of quaternary ammonium group, the side reaction of Hofmann degradation is very easily there is when being heated, cause coming off or changing weak base group into by highly basic group of quaternary ammonium group, cause the inactivation of strong anion-exchange resin, so the use temperature of quaternary ammonium fundamental mode strong alkali resin is only limitted to less than 60 DEG C, its thermotolerance is the key issue in application always.
Summary of the invention
The present invention proposes a kind of preparation method of heat-resisting strong basic type anion-exchange resin, resistance toheat is very excellent, and productive rate is high, and adsorptive capacity is high,
The preparation method of a kind of heat-resisting strong basic type anion-exchange resin that the present invention proposes, comprises the steps:
S1, ceramic particle sent into sodium hydroxide solution and soak, deionized water wash, dries, and add water, silane coupling agent stirs, whipping temp is 120-135 DEG C, and being dried to water content is 2-5wt%, and add silicon carbide grinding, toluene wash, obtains the first prefabricated material;
S2, Jiang Shui, gelatin, sodium phosphate mix, and obtain aqueous phase; Vinylbenzene, divinylbenzene, benzoyl peroxide, toluene are mixed, obtains oil phase, aqueous phase is heated up, add oil phase and stir, add ethylene dichloride, sulfuryl chloride stirs, whipping temp is 80-86 DEG C, is cooled to room temperature, with ethylene dichloride washing, filter, obtain the second prefabricated material;
S3, by the second prefabricated material, ethylene dichloride, two decyl tertiary amine mix and blend, whipping temp is 88-94 DEG C, filters, washing, dry, send in DMF swelling, add 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate stir, whipping temp is 70-80 DEG C, is cooled to room temperature, filters, washing, obtains the 3rd prefabricated material;
S4, in the 3rd prefabricated material, add oil of mirbane, anhydrous AlCl3, stearyl chloride; stirred under nitrogen atmosphere; filter; deionized water wash; add hydrochloric acid to stir; deionized water wash, dry, add ethylene dichloride, chlorination myrceane, sodium hydroxide stirring; whipping temp is 40-48 DEG C; filter, add dehydrated alcohol, chlorinated aromatic hydrocarbons, the first prefabricated material stirring, whipping temp is 70-85 DEG C; be cooled to room temperature; adopt ethanol, deionized water wash successively, dry, obtain heat-resisting strong basic type anion-exchange resin.
Preferably, in S1, the weight ratio of ceramic particle and silane coupling agent is 20-50:1-3.
Preferably, in S2, the weight ratio of vinylbenzene, divinylbenzene, benzoyl peroxide, toluene, sulfuryl chloride and 1,6-dicyanogen methyl isophorone guanidine radicals hexane is 30-60:2-8:0.2-0.8:5-10:2-10:5-15.
Preferably, in S3, the second prefabricated material is 15-30:2-5 with the weight ratio of two decyl tertiary amine.
Preferably, in S4, the weight ratio of the 3rd prefabricated material, stearyl chloride, chlorination myrceane, chlorinated aromatic hydrocarbons and the first prefabricated material is 20-40:4-9:1-2:20-40:5-15.
Preferably, in S1, by weight 20-50 part ceramic particle is sent into the sodium hydroxide solution immersion 5-10h that 60-80 part concentration is 1.5-2.5mol/L, adopt deionized water wash 2-5 time, dry, add 20-50 part water, 1-3 part silane coupling agent stirs, whipping temp is 120-135 DEG C, churning time is 20-35min, being dried to water content is 2-5wt%, and add 5-10 part silicon carbide and grind, milling time is 5-25min, by toluene wash 2-5 time, obtain the first prefabricated material.
Preferably, in S2, by weight by 60-80 part water, 1-3 part gelatin, 1-3 part sodium phosphate mix and blend, churning time is 60-100min, and whipping temp is 45-55 DEG C, obtains aqueous phase; 30-60 part vinylbenzene, 2-8 part divinylbenzene, 0.2-0.8 part benzoyl peroxide, 5-10 part toluene are mixed, obtain oil phase, be warming up to 85-95 DEG C by under aqueous phase whipped state, add oil phase and stir 1-2h, add 50-70 part ethylene dichloride, 2-10 part sulfuryl chloride stirs, whipping temp is 80-86 DEG C, churning time is 20-30h, is cooled to room temperature, with ethylene dichloride washing 2-5 time, filter, obtain the second prefabricated material.
Preferably, in S3, by weight prefabricated for 15-30 part second material, 20-40 part ethylene dichloride, the two decyl tertiary amine of 2-5 part are stirred, whipping temp is 88-94 DEG C, and churning time is 5-20h, filters, washing, dries, and sends into swelling 5-15h in 25-50 part DMF, add 5-15 part 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate that 8-10 part concentration is 1-3mol/L stirs 5-15h, whipping temp is 70-80 DEG C, be cooled to room temperature, filter, washing, obtains the 3rd prefabricated material.
Preferably, in S4, 50-70 part oil of mirbane is added by weight in the prefabricated material of 20-40 part the 3rd, 0.5-1.5 part anhydrous AlCl3, 4-9 part stearyl chloride, stirred under nitrogen atmosphere, churning time 10-25h, filter, deionized water wash 3-6 time, add the hydrochloric acid stirring 8-16h that 30-60 part concentration is 1.5-2.5mol/L, deionized water wash 2-5 time, dry, add 30-50 part ethylene dichloride, 1-2 part chlorination myrceane, 1-3 part sodium hydroxide stirs, whipping temp is 40-48 DEG C, churning time is 20-40h, filter, add 20-40 part dehydrated alcohol, 20-40 part chlorinated aromatic hydrocarbons, the prefabricated material of 5-15 part first stirs, whipping temp is 70-85 DEG C, churning time is 5-15h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
Preferably, the preparation method of described heat-resisting strong basic type anion-exchange resin, comprises the steps:
S1, the sodium hydroxide solution being 2-2.3mol/L by 40-46 part ceramic particle feeding 70-76 part concentration by weight soak 6-8h, adopt deionized water wash 3-4 time, dry, add 30-45 part water, 2-2.6 part silane coupling agent stirs, whipping temp is 125-130 DEG C, churning time is 28-30min, being dried to water content is 3-4wt%, and add 6-8 part silicon carbide and grind, milling time is 10-16min, by toluene wash 2-5 time, obtain the first prefabricated material;
S2,70-76 part water, 2-2.4 part gelatin, 2-2.8 part sodium phosphate are sent in reactor and stir 80-90min by weight, whipping temp is 50-54 DEG C, obtains aqueous phase; 50-56 part vinylbenzene, 4-6 part divinylbenzene, 0.4-0.5 part benzoyl peroxide, 6-8 part toluene are mixed, obtain oil phase, be warming up to 88-90 DEG C by under aqueous phase whipped state, add oil phase and stir 1.5-2h, add 60-64 part ethylene dichloride, 4-6 part sulfuryl chloride stirs, whipping temp is 82-84 DEG C, churning time is 24-26h, is cooled to room temperature, with ethylene dichloride washing 2-5 time, filter, obtain the second prefabricated material;
S3, prefabricated for 20-24 part second material, 30-36 part ethylene dichloride, the two decyl tertiary amine of 3-3.6 part are stirred by weight, whipping temp is 90-93 DEG C, and churning time is 10-14h, filter, washing, dry, send into swelling 10-13h in 40-46 part DMF, add 8-12 part 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate that 9-9.6 part concentration is 2-2.4mol/L stirs 10-12h, whipping temp is 74-76 DEG C, be cooled to room temperature, filter, washing, obtains the 3rd prefabricated material;
S4, 60-64 part oil of mirbane is added by weight in the prefabricated material of 30-36 part the 3rd, 0.8-1.2 part anhydrous AlCl3, 5-5.6 part stearyl chloride, stirred under nitrogen atmosphere, churning time 20-23h, filter, deionized water wash 3-6 time, add the hydrochloric acid stirring 10-12h that 40-50 part concentration is 2-2.3mol/L, deionized water wash 2-5 time, dry, add 40-46 part ethylene dichloride, 1.2-1.5 part chlorination myrceane, 2-2.4 part sodium hydroxide stirs, whipping temp is 42-44 DEG C, churning time is 30-36h, filter, add 30-36 part dehydrated alcohol, 30-34 part chlorinated aromatic hydrocarbons, the prefabricated material of 8-10 part first stirs, whipping temp is 80-82 DEG C, churning time is 10-13h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
In the present invention, adopt vinylbenzene, it is skeleton that Vinylstyrene stirring polymerization obtains microballoon, add sulfuryl chloride and carry out acylation reaction, introduce chlorsulfonic acid base, carry out amination reaction adding two decyl tertiary amine, carry out quaternary ammoniated to it again, goods yield is high, side reaction is few, heat-resistant stability is good, the modified ceramic particle added can be had an effect with matrix resin, and load is in resin, it is coarse that the surface of resin becomes, reference area increases further, and modified ceramic particle itself has adsorption, act synergistically with matrix resin, the loading capacity of resin is very excellent.
1, in 6-dicyanogen methyl isophorone guanidine radicals hexane, three C-N bond distances of guanidine radicals are identical, than general C-N key or C=N short, this there is conjugative effect by guanidine radicals, make positive charge complete evenly distribute on three nitrogen-atoms, thus make bond distance's equalization, the compound with this structure is very stable beyond doubt, therefore guanidine radicals has and accepts hydrogen ion to form the strong tendency of this rock steady structure, by being bonded on the skeleton of resin by 1,6-dicyanogen methyl isophorone guanidine radicals hexane single step reaction, goods thermostability is very excellent, and productive rate is higher; Wherein stearyl chloride and prefabricated material effect, reactant polarity is high, good hydrophilic property, and react with chlorination myrceane further, synthesize the exchange resin with two long-chain, not only increased steric hindrance in duct, reduced reaction intermediate and be deposited on duct, shorten the reaction times, and thermostability strengthens further.
Test goods, the highly basic exchange capacity of goods is 2-2.3mmol/g, and after thermal stability test, the rate of loss of resin highly basic exchange capacity is 2.1-2.6%.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A preparation method for heat-resisting strong basic type anion-exchange resin, comprises the steps:
S1, ceramic particle sent into sodium hydroxide solution and soak, deionized water wash, dries, and add water, silane coupling agent stirs, whipping temp is 131 DEG C, and being dried to water content is 2.5wt%, and add silicon carbide grinding, toluene wash, obtains the first prefabricated material;
S2, Jiang Shui, gelatin, sodium phosphate mix, and obtain aqueous phase; Vinylbenzene, divinylbenzene, benzoyl peroxide, toluene are mixed, obtains oil phase, aqueous phase is heated up, add oil phase and stir, add ethylene dichloride, sulfuryl chloride stirs, whipping temp is 82 DEG C, is cooled to room temperature, with ethylene dichloride washing, filter, obtain the second prefabricated material;
S3, by the second prefabricated material, ethylene dichloride, two decyl tertiary amine mix and blend, whipping temp is 91 DEG C, filters, washing, dry, send in DMF swelling, add 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate stir, whipping temp is 76 DEG C, is cooled to room temperature, filters, washing, obtains the 3rd prefabricated material;
S4, in the 3rd prefabricated material, add oil of mirbane, anhydrous AlCl3, stearyl chloride; stirred under nitrogen atmosphere; filter; deionized water wash; add hydrochloric acid to stir; deionized water wash, dry, add ethylene dichloride, chlorination myrceane, sodium hydroxide stirring; whipping temp is 45 DEG C; filter, add dehydrated alcohol, chlorinated aromatic hydrocarbons, the first prefabricated material stirring, whipping temp is 72 DEG C; be cooled to room temperature; adopt ethanol, deionized water wash successively, dry, obtain heat-resisting strong basic type anion-exchange resin.
Embodiment 2
A preparation method for heat-resisting strong basic type anion-exchange resin, comprises the steps:
S1, by weight 20 parts of ceramic particles are sent into 80 parts of concentration be 1.5mol/L sodium hydroxide solution soak 10h, deionized water wash is adopted to dry for 2 times, add 50 parts of water, 1 part of silane coupling agent stirs, whipping temp is 135 DEG C, and churning time is 20min, and being dried to water content is 5wt%, add 5 parts of silicon carbide to grind, milling time is 25min, by toluene wash 2 times, obtains the first prefabricated material;
S2,80 parts of water, 1 part of gelatin, 3 parts of sodium phosphates are sent in reactors and stir 60min by weight, whipping temp is 55 DEG C, obtains aqueous phase; 30 parts of vinylbenzene, 8 parts of divinylbenzenes, 0.2 part of benzoyl peroxide, 10 parts of toluene are mixed, obtain oil phase, be warming up to 85 DEG C by under aqueous phase whipped state, add oil phase and stir 2h, add 50 parts of ethylene dichloride, 10 parts of sulfuryl chlorides stir, whipping temp is 80 DEG C, churning time is 30h, is cooled to room temperature, washs 2 times with ethylene dichloride, filter, obtain the second prefabricated material;
S3,30 part of second prefabricated material, 20 parts of ethylene dichloride, 5 parts of two decyl tertiary amines are stirred by weight, whipping temp is 88 DEG C, and churning time is 20h, filter, washing, dry, send into swelling 15h in 25 parts of DMF, add 5 part of 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate that 10 parts of concentration are 1mol/L stirs 15h, whipping temp is 70 DEG C, be cooled to room temperature, filter, washing, obtains the 3rd prefabricated material;
S4, 50 parts of oil of mirbane are added by weight in 40 part of the 3rd prefabricated material, 1.5 parts of anhydrous AlCl3s, 4 parts of stearyl chlorides, stirred under nitrogen atmosphere, churning time 25h, filter, deionized water wash 3 times, add the hydrochloric acid stirring 16h that 60 parts of concentration are 1.5mol/L, deionized water wash 2 times, dry, add 50 parts of ethylene dichloride, 1 part of chlorination myrceane, 3 parts of sodium hydroxide stir, whipping temp is 40 DEG C, churning time is 40h, filter, add 20 parts of dehydrated alcohols, 40 parts of chlorinated aromatic hydrocarbons, 5 part of first prefabricated material stirs, whipping temp is 85 DEG C, churning time is 5h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
Embodiment 3
A preparation method for heat-resisting strong basic type anion-exchange resin, comprises the steps:
S1, by weight 50 parts of ceramic particles are sent into 60 parts of concentration be 2.5mol/L sodium hydroxide solution soak 5h, deionized water wash is adopted to dry for 5 times, add 20 parts of water, 3 parts of silane coupling agents stir, whipping temp is 120 DEG C, and churning time is 35min, and being dried to water content is 2wt%, add 10 parts of silicon carbide to grind, milling time is 5min, by toluene wash 5 times, obtains the first prefabricated material;
S2,60 parts of water, 3 parts of gelatin, 1 part of sodium phosphate are sent in reactor and stir 100min by weight, whipping temp is 45 DEG C, obtains aqueous phase; 60 parts of vinylbenzene, 2 parts of divinylbenzenes, 0.8 part of benzoyl peroxide, 5 parts of toluene are mixed, obtain oil phase, be warming up to 95 DEG C by under aqueous phase whipped state, add oil phase and stir 1h, add 70 parts of ethylene dichloride, 2 parts of sulfuryl chlorides stir, whipping temp is 86 DEG C, churning time is 20h, is cooled to room temperature, washs 5 times with ethylene dichloride, filter, obtain the second prefabricated material;
S3,15 part of second prefabricated material, 40 parts of ethylene dichloride, 2 parts of two decyl tertiary amines are stirred by weight, whipping temp is 94 DEG C, and churning time is 5h, filter, washing, dry, send into swelling 5h in 50 parts of DMF, add 15 part of 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate that 8 parts of concentration are 3mol/L stirs 5h, whipping temp is 80 DEG C, be cooled to room temperature, filter, washing, obtains the 3rd prefabricated material;
S4, 70 parts of oil of mirbane are added by weight in 20 part of the 3rd prefabricated material, 0.5 part of anhydrous AlCl3, 9 parts of stearyl chlorides, stirred under nitrogen atmosphere, churning time 10h, filter, deionized water wash 6 times, add the hydrochloric acid stirring 8h that 30 parts of concentration are 2.5mol/L, deionized water wash 5 times, dry, add 30 parts of ethylene dichloride, 2 parts of chlorination myrceanes, 1 part of sodium hydroxide stirs, whipping temp is 48 DEG C, churning time is 20h, filter, add 40 parts of dehydrated alcohols, 20 parts of chlorinated aromatic hydrocarbons, 15 part of first prefabricated material stirs, whipping temp is 70 DEG C, churning time is 15h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
Embodiment 4
A preparation method for heat-resisting strong basic type anion-exchange resin, comprises the steps:
S1, by weight 42 parts of ceramic particles are sent into 72 parts of concentration be 2.1mol/L sodium hydroxide solution soak 8h, deionized water wash is adopted to dry for 3 times, add 40 parts of water, 2.5 parts of silane coupling agents stir, whipping temp is 132 DEG C, and churning time is 32min, and being dried to water content is 3.5wt%, add 8 parts of silicon carbide to grind, milling time is 15min, by toluene wash 3 times, obtains the first prefabricated material;
S2,72 parts of water, 2.4 parts of gelatin, 1.6 parts of sodium phosphates are sent in reactors and stir 82min by weight, whipping temp is 52 DEG C, obtains aqueous phase; 52 parts of vinylbenzene, 4 parts of divinylbenzenes, 0.6 part of benzoyl peroxide, 8 parts of toluene are mixed, obtain oil phase, be warming up to 92 DEG C by under aqueous phase whipped state, add oil phase and stir 1.5h, add 62 parts of ethylene dichloride, 8 parts of sulfuryl chlorides stir, whipping temp is 84 DEG C, churning time is 24h, is cooled to room temperature, washs 3 times with ethylene dichloride, filter, obtain the second prefabricated material;
S3,24 part of second prefabricated material, 36 parts of ethylene dichloride, 2.8 parts of two decyl tertiary amines are stirred by weight, whipping temp is 90 DEG C, and churning time is 12h, filter, washing, dry, send into swelling 8h in 36 parts of DMF, add 12 part of 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate that 9 parts of concentration are 2.4mol/L stirs 12h, whipping temp is 78 DEG C, be cooled to room temperature, filter, washing, obtains the 3rd prefabricated material;
S4, 62 parts of oil of mirbane are added by weight in 24 part of the 3rd prefabricated material, 1.2 parts of anhydrous AlCl3s, 5 parts of stearyl chlorides, stirred under nitrogen atmosphere, churning time 20h, filter, deionized water wash 4 times, add the hydrochloric acid stirring 12h that 55 parts of concentration are 2.1mol/L, deionized water wash 3 times, dry, add 42 parts of ethylene dichloride, 1.4 parts of chlorination myrceanes, 1.5 parts of sodium hydroxide stir, whipping temp is 42 DEG C, churning time is 26h, filter, add 30 parts of dehydrated alcohols, 36 parts of chlorinated aromatic hydrocarbons, 12 part of first prefabricated material stirs, whipping temp is 82 DEG C, churning time is 12h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a preparation method for heat-resisting strong basic type anion-exchange resin, is characterized in that, comprises the steps:
S1, ceramic particle sent into sodium hydroxide solution and soak, deionized water wash, dries, and add water, silane coupling agent stirs, whipping temp is 120-135 DEG C, and being dried to water content is 2-5wt%, and add silicon carbide grinding, toluene wash, obtains the first prefabricated material;
S2, Jiang Shui, gelatin, sodium phosphate mix, and obtain aqueous phase; Vinylbenzene, divinylbenzene, benzoyl peroxide, toluene are mixed, obtains oil phase, aqueous phase is heated up, add oil phase and stir, add ethylene dichloride, sulfuryl chloride stirs, whipping temp is 80-86 DEG C, is cooled to room temperature, with ethylene dichloride washing, filter, obtain the second prefabricated material;
S3, by the second prefabricated material, ethylene dichloride, two decyl tertiary amine mix and blend, whipping temp is 88-94 DEG C, filters, washing, dry, send in DMF swelling, add 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate stir, whipping temp is 70-80 DEG C, is cooled to room temperature, filters, washing, obtains the 3rd prefabricated material;
S4, in the 3rd prefabricated material, add oil of mirbane, anhydrous AlCl3, stearyl chloride; stirred under nitrogen atmosphere; filter; deionized water wash; add hydrochloric acid to stir; deionized water wash, dry, add ethylene dichloride, chlorination myrceane, sodium hydroxide stirring; whipping temp is 40-48 DEG C; filter, add dehydrated alcohol, chlorinated aromatic hydrocarbons, the first prefabricated material stirring, whipping temp is 70-85 DEG C; be cooled to room temperature; adopt ethanol, deionized water wash successively, dry, obtain heat-resisting strong basic type anion-exchange resin.
2. the preparation method of heat-resisting strong basic type anion-exchange resin according to claim 1, is characterized in that, in S1, the weight ratio of ceramic particle and silane coupling agent is 20-50:1-3.
3. the preparation method of heat-resisting strong basic type anion-exchange resin according to claim 1 and 2, it is characterized in that, in S2, the weight ratio of vinylbenzene, divinylbenzene, benzoyl peroxide, toluene, sulfuryl chloride and 1,6-dicyanogen methyl isophorone guanidine radicals hexane is 30-60:2-8:0.2-0.8:5-10:2-10:5-15.
4. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-3, is characterized in that, in S3, the second prefabricated material is 15-30:2-5 with the weight ratio of two decyl tertiary amine.
5. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-4, it is characterized in that, in S4, the weight ratio of the 3rd prefabricated material, stearyl chloride, chlorination myrceane, chlorinated aromatic hydrocarbons and the first prefabricated material is 20-40:4-9:1-2:20-40:5-15.
6. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-5, it is characterized in that, in S1, by weight 20-50 part ceramic particle is sent into the sodium hydroxide solution immersion 5-10h that 60-80 part concentration is 1.5-2.5mol/L, adopt deionized water wash 2-5 time, dry, add 20-50 part water, 1-3 part silane coupling agent stirs, whipping temp is 120-135 DEG C, churning time is 20-35min, being dried to water content is 2-5wt%, add 5-10 part silicon carbide to grind, milling time is 5-25min, by toluene wash 2-5 time, obtain the first prefabricated material.
7. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-6, it is characterized in that, in S2, by weight by 60-80 part water, 1-3 part gelatin, 1-3 part sodium phosphate mix and blend, churning time is 60-100min, whipping temp is 45-55 DEG C, obtains aqueous phase; 30-60 part vinylbenzene, 2-8 part divinylbenzene, 0.2-0.8 part benzoyl peroxide, 5-10 part toluene are mixed, obtain oil phase, be warming up to 85-95 DEG C by under aqueous phase whipped state, add oil phase and stir 1-2h, add 50-70 part ethylene dichloride, 2-10 part sulfuryl chloride stirs, whipping temp is 80-86 DEG C, churning time is 20-30h, is cooled to room temperature, with ethylene dichloride washing 2-5 time, filter, obtain the second prefabricated material.
8. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-7, it is characterized in that, in S3, by weight by prefabricated for 15-30 part second material, 20-40 part ethylene dichloride, the two decyl tertiary amine of 2-5 part stirs, whipping temp is 88-94 DEG C, churning time is 5-20h, filter, washing, dry, send into swelling 5-15h in 25-50 part DMF, add 5-15 part 1, 6-dicyanogen methyl isophorone guanidine radicals hexane, 8-10 part concentration is that the sodium ethylate of 1-3mol/L stirs 5-15h, whipping temp is 70-80 DEG C, be cooled to room temperature, filter, washing, obtain the 3rd prefabricated material.
9. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-8, it is characterized in that, in S4, 50-70 part oil of mirbane is added by weight in the prefabricated material of 20-40 part the 3rd, 0.5-1.5 part anhydrous AlCl3, 4-9 part stearyl chloride, stirred under nitrogen atmosphere, churning time 10-25h, filter, deionized water wash 3-6 time, add the hydrochloric acid stirring 8-16h that 30-60 part concentration is 1.5-2.5mol/L, deionized water wash 2-5 time, dry, add 30-50 part ethylene dichloride, 1-2 part chlorination myrceane, 1-3 part sodium hydroxide stirs, whipping temp is 40-48 DEG C, churning time is 20-40h, filter, add 20-40 part dehydrated alcohol, 20-40 part chlorinated aromatic hydrocarbons, the prefabricated material of 5-15 part first stirs, whipping temp is 70-85 DEG C, churning time is 5-15h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
10. the preparation method of the heat-resisting strong basic type anion-exchange resin according to any one of claim 1-9, is characterized in that, comprise the steps:
S1, the sodium hydroxide solution being 2-2.3mol/L by 40-46 part ceramic particle feeding 70-76 part concentration by weight soak 6-8h, adopt deionized water wash 3-4 time, dry, add 30-45 part water, 2-2.6 part silane coupling agent stirs, whipping temp is 125-130 DEG C, churning time is 28-30min, being dried to water content is 3-4wt%, and add 6-8 part silicon carbide and grind, milling time is 10-16min, by toluene wash 2-5 time, obtain the first prefabricated material;
S2,70-76 part water, 2-2.4 part gelatin, 2-2.8 part sodium phosphate are sent in reactor and stir 80-90min by weight, whipping temp is 50-54 DEG C, obtains aqueous phase; 50-56 part vinylbenzene, 4-6 part divinylbenzene, 0.4-0.5 part benzoyl peroxide, 6-8 part toluene are mixed, obtain oil phase, be warming up to 88-90 DEG C by under aqueous phase whipped state, add oil phase and stir 1.5-2h, add 60-64 part ethylene dichloride, 4-6 part sulfuryl chloride stirs, whipping temp is 82-84 DEG C, churning time is 24-26h, is cooled to room temperature, with ethylene dichloride washing 2-5 time, filter, obtain the second prefabricated material;
S3, prefabricated for 20-24 part second material, 30-36 part ethylene dichloride, the two decyl tertiary amine of 3-3.6 part are stirred by weight, whipping temp is 90-93 DEG C, and churning time is 10-14h, filter, washing, dry, send into swelling 10-13h in 40-46 part DMF, add 8-12 part 1,6-dicyanogen methyl isophorone guanidine radicals hexane, sodium ethylate that 9-9.6 part concentration is 2-2.4mol/L stirs 10-12h, whipping temp is 74-76 DEG C, be cooled to room temperature, filter, washing, obtains the 3rd prefabricated material;
S4, 60-64 part oil of mirbane is added by weight in the prefabricated material of 30-36 part the 3rd, 0.8-1.2 part anhydrous AlCl3, 5-5.6 part stearyl chloride, stirred under nitrogen atmosphere, churning time 20-23h, filter, deionized water wash 3-6 time, add the hydrochloric acid stirring 10-12h that 40-50 part concentration is 2-2.3mol/L, deionized water wash 2-5 time, dry, add 40-46 part ethylene dichloride, 1.2-1.5 part chlorination myrceane, 2-2.4 part sodium hydroxide stirs, whipping temp is 42-44 DEG C, churning time is 30-36h, filter, add 30-36 part dehydrated alcohol, 30-34 part chlorinated aromatic hydrocarbons, the prefabricated material of 8-10 part first stirs, whipping temp is 80-82 DEG C, churning time is 10-13h, be cooled to room temperature, adopt ethanol successively, deionized water wash, dry, obtain heat-resisting strong basic type anion-exchange resin.
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Application publication date: 20151223 |